JP5446381B2 - Rubber composition for tire tread - Google Patents
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- JP5446381B2 JP5446381B2 JP2009082171A JP2009082171A JP5446381B2 JP 5446381 B2 JP5446381 B2 JP 5446381B2 JP 2009082171 A JP2009082171 A JP 2009082171A JP 2009082171 A JP2009082171 A JP 2009082171A JP 5446381 B2 JP5446381 B2 JP 5446381B2
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- 229920001971 elastomer Polymers 0.000 title claims description 47
- 239000005060 rubber Substances 0.000 title claims description 47
- 239000000203 mixture Substances 0.000 title claims description 45
- 239000011347 resin Substances 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 55
- 239000005077 polysulfide Substances 0.000 claims description 25
- 229920001021 polysulfide Polymers 0.000 claims description 25
- 150000008117 polysulfides Polymers 0.000 claims description 25
- 125000004122 cyclic group Chemical group 0.000 claims description 23
- 150000003505 terpenes Chemical class 0.000 claims description 19
- 235000007586 terpenes Nutrition 0.000 claims description 19
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 16
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- 229920003244 diene elastomer Polymers 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- -1 pentaerythritol ester Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- 150000000133 (4R)-limonene derivatives Chemical class 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NLXGURFLBLRZRO-UHFFFAOYSA-N 1-chloro-2-(2-chloroethoxymethoxy)ethane Chemical compound ClCCOCOCCCl NLXGURFLBLRZRO-UHFFFAOYSA-N 0.000 description 1
- HBKBEZURJSNABK-MWJPAGEPSA-N 2,3-dihydroxypropyl (1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(=O)OCC(O)CO HBKBEZURJSNABK-MWJPAGEPSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤトレッド用ゴム組成物に関し、更に詳しくは、耐摩耗性を維持しながら走行初期からのドライグリップ性能を向上し、そのドライグリップ性能の持続性を長くすると共に、耐ブローアウト性を向上するようにしたタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for a tire tread, and more specifically, while improving the dry grip performance from the beginning of running while maintaining the wear resistance, the durability of the dry grip performance is increased and the blowout resistance is improved. The present invention relates to a rubber composition for a tire tread that is improved.
空気入りタイヤのグリップ性能は、タイヤ温度の影響が大きく、低温状態では十分なグリップ性能が得られないことが知られている。特に、競技用タイヤでは、トレッドを構成するゴム組成物が、走行開始後、できるだけ早く高温状態に達するような特性を備え、優れたドライグリップ性能を早期に発揮することが要求されている。このため、トレッド用ゴム組成物にカーボンブラック等の充填剤を多量に配合するようにしている。しかし、充填剤を多量に配合したゴム組成物は、高速走行が長時間になると熱ダレ現象を起こし、ドライグリップ性能が徐々に低下し、ついにはブローアウトしてしまうという問題があった。 It is known that the grip performance of a pneumatic tire is greatly affected by the tire temperature, and sufficient grip performance cannot be obtained at low temperatures. In particular, in a racing tire, it is required that the rubber composition constituting the tread has characteristics that reach a high temperature state as soon as possible after the start of running, and exhibits excellent dry grip performance at an early stage. For this reason, a large amount of filler such as carbon black is blended in the rubber composition for tread. However, the rubber composition containing a large amount of the filler has a problem that when it runs at a high speed for a long time, it causes a thermal sag phenomenon, the dry grip performance gradually decreases, and eventually blows out.
空気入りタイヤのグリップ性能を改善するため、特許文献１は、スチレンブタジエンゴムに、低分子量のスチレン−ブタジエン共重合体、ポリイソプレン等から選ばれる液状ポリマー又はロジン系樹脂、テルペン系樹脂等の粘着付与性を有する樹脂を配合したタイヤ用ゴム組成物を提案している。しかしながら、このタイヤ用ゴム組成物は、ドライグリップ性能の持続性及び耐ブローアウト性については、まだ改善の余地があった。また、粘着性付与樹脂を配合すると耐摩耗性が悪化するという問題があった。 In order to improve the grip performance of a pneumatic tire, Patent Document 1 discloses adhesion of styrene butadiene rubber to a liquid polymer selected from a low molecular weight styrene-butadiene copolymer, polyisoprene, rosin resin, terpene resin, and the like. A tire rubber composition containing a resin having an imparting property is proposed. However, this tire rubber composition still has room for improvement in terms of durability of dry grip performance and blowout resistance. Moreover, when tackifying resin was mix | blended, there existed a problem that abrasion resistance deteriorated.
本発明の目的は、耐摩耗性を維持しながら走行初期からのドライグリップ性能を向上し、そのドライグリップ性能の持続性を長くすると共に、耐ブローアウト性を向上するようにしたタイヤトレッド用ゴム組成物を提供することにある。 The object of the present invention is to improve the dry grip performance from the beginning of running while maintaining the wear resistance, and to increase the durability of the dry grip performance and improve the blowout resistance. It is to provide a composition.
上記目的を達成する本発明のタイヤトレッド用ゴム組成物は、ジエン系ゴム１００重量部に対し、粘着性付与樹脂を２０〜６０重量部、下記式（Ｉ）で示される環状ポリスルフィドを１〜１０重量部、窒素吸着比表面積（Ｎ 2 ＳＡ）が２２０〜３５０ｍ 2 ／ｇであるカーボンブラックを１００〜１５０重量部及び硫黄を配合し、前記ジエン系ゴムがスチレン−ブタジエンゴムであり、前記硫黄に対する前記環状ポリスルフィドの重量比（環状ポリスルフィド／硫黄）が、３／１〜１０／１であることを特徴とする。 The rubber composition for a tire tread of the present invention that achieves the above-mentioned object has 20 to 60 parts by weight of a tackifier resin and 1 to 10 of a cyclic polysulfide represented by the following formula (I) with respect to 100 parts by weight of a diene rubber. 100 parts by weight of carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 220 to 350 m 2 / g and sulfur are blended, and the diene rubber is a styrene-butadiene rubber. The weight ratio of the cyclic polysulfide (cyclic polysulfide / sulfur) is 3/1 to 10/1 .
前記粘着性付与樹脂は、軟化点が１００〜１７０℃であることが好ましく、テルペンフェノール樹脂、テルペンスチレン樹脂、芳香族変性テルペン樹脂又はロジン系樹脂であるとよい。 The tackifying resin preferably has a softening point of 100 to 170 ° C., and is preferably a terpene phenol resin, a terpene styrene resin, an aromatic modified terpene resin, or a rosin resin.
このタイヤトレッド用ゴム組成物を使用した空気入りタイヤは、耐摩耗性を維持しながら走行初期のドライグリップ性能が優れ、そのドライグリップ性能を長く持続し、耐ブローアウト性に優れる。 A pneumatic tire using the rubber composition for a tire tread has excellent dry grip performance at the beginning of running while maintaining wear resistance, and the dry grip performance is maintained for a long time, and is excellent in blowout resistance.
本発明のタイヤトレッド用ゴム組成物は、ジエン系ゴム１００重量部に対し、粘着性付与樹脂を２０〜６０重量部配合したことにより、走行初期のドライグリップ性能を早期に立ち上げることができる。また、前記式（Ｉ）で示された環状ポリスルフィドを１〜１０重量部配合したことにより、優れたドライグリップ性能を長く持続すると共に、耐ブローアウト性を向上することができる。また、環状ポリスルフィドを配合することにより、粘着性付与樹脂の配合に伴う耐摩耗性の低下を可及的に小さくすることができる。 The rubber composition for a tire tread of the present invention can start up dry grip performance at an early stage of running early by blending 20 to 60 parts by weight of tackifier resin with respect to 100 parts by weight of diene rubber. In addition, by blending 1 to 10 parts by weight of the cyclic polysulfide represented by the formula (I), excellent dry grip performance can be maintained for a long time and blowout resistance can be improved. Further, by blending the cyclic polysulfide, it is possible to minimize the decrease in wear resistance accompanying the blending of the tackifying resin.
本発明のタイヤトレッド用ゴム組成物において、ゴム成分はジエン系ゴムである。ジエン系ゴムとしては、スチレン−ブタジエンゴムを使用する。 In the rubber composition for a tire tread of the present invention, the rubber component is a diene rubber. Examples of the diene rubber, scan styrene - to use butadiene rubber.
ジエン系ゴムとしてスチレン−ブタジエンゴムを用いることにより、グリップ性能を向上することができる。特に、ガラス転移温度が好ましくは−３５℃以上、より好ましくは−３０℃〜−１０℃のスチレン−ブタジエンゴムが好ましい。このようなスチレン−ブタジエンゴムを配合することにより、長時間の高速走行時におけるグリップ性能の低下を抑制する。なお、スチレンブタジエンゴムのガラス転移温度が高過ぎると、発熱性が大きくなるまでに時間がかかりドライグリップ性能を早期に立上げることができない。スチレンブタジエンゴムのガラス転移温度は、示差走査熱量測定（ＤＳＣ）により２０℃／分の昇温速度条件によりサーモグラムを測定し、転移域の中点の温度とする。なお、スチレンブタジエンゴムが油展品である場合には、オイルを除いた原料ゴムのガラス転移温度とする。 Grip performance can be improved by using styrene-butadiene rubber as the diene rubber. In particular, a styrene-butadiene rubber having a glass transition temperature of preferably −35 ° C. or higher, more preferably −30 ° C. to −10 ° C. is preferable. By blending such styrene-butadiene rubber, it is possible to suppress a decrease in grip performance during long-time high speed running. If the glass transition temperature of the styrene butadiene rubber is too high, it takes time until the heat build-up becomes large, and the dry grip performance cannot be brought up early. The glass transition temperature of the styrene butadiene rubber is measured by a differential scanning calorimetry (DSC) under a temperature increase rate condition of 20 ° C./min, and is set as the temperature at the midpoint of the transition region. When the styrene butadiene rubber is an oil-extended product, the glass transition temperature of the raw rubber excluding the oil is used.
本発明のタイヤトレッド用ゴム組成物は、粘着性付与樹脂を配合することにより走行初期のドライグリップ性能を向上する。粘着性付与樹脂の配合量は、ジエン系ゴム１００重量部に対し２０〜６０重量部、好ましくは２０〜５０重量部である。粘着性付与樹脂の配合量が２０重量部未満であると、走行初期のドライグリップ性能を十分に高くすることができない。また、粘着性付与樹脂の配合量が６０重量部を超えると、ドライグリップ性能の持続性及び耐ブローアウト性能が低下する。また、ゴム組成物の耐摩耗性が悪化する。さらに、ゴム組成物のロールへの密着性が増大するため、加工性が悪化する。なお、粘着性付与樹脂は軟化剤としての作用も行うため、粘着性付与樹脂の配合量に応じて、アロマオイル等の他の軟化剤の配合量を加減するとよい。 The rubber composition for a tire tread of the present invention improves the dry grip performance at the beginning of running by blending a tackifier resin. The compounding quantity of tackifying resin is 20-60 weight part with respect to 100 weight part of diene rubbers, Preferably it is 20-50 weight part. If the compounding amount of the tackifying resin is less than 20 parts by weight, the dry grip performance at the beginning of running cannot be sufficiently increased. Moreover, when the compounding quantity of tackifying resin exceeds 60 weight part, the sustainability of dry grip performance and blowout-proof performance will fall. In addition, the wear resistance of the rubber composition is deteriorated. Furthermore, since the adhesiveness of the rubber composition to the roll increases, processability deteriorates. In addition, since tackifying resin also acts as a softening agent, the blending amount of other softening agents such as aroma oil may be adjusted depending on the blending amount of the tackifying resin.
本発明において、粘着性付与樹脂とは、ゴム組成物への粘着付与性を有する樹脂であり、一般には分子量が数百から数千の熱可塑性樹脂で、上述したジエン系ゴムに配合することによって粘着性を付与する作用を行う。粘着性付与樹脂としては、例えば、テルペン系樹脂、ロジン系樹脂などの天然樹脂、石油系樹脂、石炭系樹脂、フェノール系樹脂、キシレン系樹脂などの合成樹脂が例示される。なかでもテルペン系樹脂、ロジン系樹脂が好ましい。 In the present invention, the tackifying resin is a resin having tackifying properties to a rubber composition, and is generally a thermoplastic resin having a molecular weight of several hundred to several thousand, and is blended with the above-described diene rubber. Performs the action of imparting tackiness. Examples of the tackifying resin include natural resins such as terpene resins and rosin resins, and synthetic resins such as petroleum resins, coal resins, phenol resins, and xylene resins. Of these, terpene resins and rosin resins are preferable.
テルペン系樹脂としては、例えばα−ピネン樹脂、β−ピネン樹脂、リモネン樹脂、水添リモネン樹脂、ジペンテン樹脂、テルペンフェノール樹脂、テルペンスチレン樹脂、芳香族変性テルペン樹脂、水素添加テルペン樹脂等が挙げられる。ロジン系樹脂としては、例えばガムロジン、トール油ロジン、ウッドロジン、水素添加ロジン、不均化ロジン、重合ロジン、マレイン化ロジンおよびフマル化ロジン等の変性ロジン、これらのロジンのグリセリンエステル、ペンタエリスリトールエステル、メチルエステルおよびトリエチレングリコールエステルなどのエステル誘導体、並びにロジン変性フェノール樹脂等が挙げられる。これらの中でも、配合されたゴム組成物の耐摩耗性とグリップ特性の観点から、テルペンフェノール樹脂、テルペンスチレン樹脂、芳香族変性テルペン樹脂、重合ロジンが好ましい。 Examples of the terpene resin include α-pinene resin, β-pinene resin, limonene resin, hydrogenated limonene resin, dipentene resin, terpene phenol resin, terpene styrene resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. . Examples of rosin resins include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin and modified rosin such as fumarinated rosin, glycerin ester of these rosin, pentaerythritol ester, Examples include ester derivatives such as methyl ester and triethylene glycol ester, and rosin-modified phenolic resin. Among these, terpene phenol resin, terpene styrene resin, aromatic modified terpene resin, and polymerized rosin are preferable from the viewpoint of wear resistance and grip characteristics of the blended rubber composition.
粘着性付与樹脂は、軟化点が好ましくは１００〜１７０℃、より好ましくは１２０〜１６５℃であるとよい。粘着性付与樹脂の軟化点が１００℃未満であると、ドライグリップ性能を向上する効果が得られなくなる。また、粘着性付与樹脂の軟化点が１７０℃を超えると、タイヤの作動性に悪影響を及ぼす。粘着性付与樹脂の軟化点は、ＪＩＳ Ｋ５９０２に準拠して測定した値とする。 The tackifying resin preferably has a softening point of 100 to 170 ° C, more preferably 120 to 165 ° C. When the softening point of the tackifying resin is less than 100 ° C., the effect of improving the dry grip performance cannot be obtained. Moreover, when the softening point of the tackifying resin exceeds 170 ° C., the operability of the tire is adversely affected. The softening point of the tackifying resin is a value measured according to JIS K5902.
本発明のタイヤトレッド用ゴム組成物は、下記式（Ｉ）で示された環状ポリスルフィドを配合することにより、高いレベルのドライグリップ性能を長く持続すると共に、耐ブローアウト性を向上する。また、環状ポリスルフィドは、高温状態におけるゴム強度を高くするため、粘着性付与樹脂を配合したときにゴム組成物の耐摩耗性が低下するのを可及的に小さくすることができる。 The rubber composition for a tire tread of the present invention blends a cyclic polysulfide represented by the following formula (I), thereby maintaining a high level of dry grip performance for a long time and improving blowout resistance. In addition, since the cyclic polysulfide increases the rubber strength at a high temperature, it is possible to reduce the wear resistance of the rubber composition as much as possible when a tackifying resin is blended.
上記式（Ｉ）の環状ポリスルフィドにおいて、Ｒがアルキレン基又はオキシアルキレン基であるとき、その炭素数は、好ましくは２〜１８、より好ましくは４〜８であるとよい。また、アルキレン基及びオキシアルキレン基に対する置換基としては、例えばフェニル基、ベンジル基、メチル基、エポキシ基、イソシアネート基、ビニル基、シリル基などを例示することができる。ｘは好ましくは平均３〜５、より好ましくは平均３．５〜４．５にするとよい。また、ｎは好ましくは１〜１５、より好ましくは１〜１０、さらに好ましくは１〜５の整数にするとよい。このような環状ポリスルフィドは、通常の方法で製造することができ、例えば特開２００７−９２０８６号公報に記載の製造方法を例示することができる。 In the cyclic polysulfide of the above formula (I), when R is an alkylene group or an oxyalkylene group, the carbon number thereof is preferably 2-18, more preferably 4-8. Moreover, as a substituent with respect to an alkylene group and an oxyalkylene group, a phenyl group, a benzyl group, a methyl group, an epoxy group, an isocyanate group, a vinyl group, a silyl group etc. can be illustrated, for example. x is preferably 3 to 5 on average, more preferably 3.5 to 4.5 on average. N is preferably an integer of 1 to 15, more preferably 1 to 10, and still more preferably 1 to 5. Such a cyclic polysulfide can be produced by an ordinary method, for example, a production method described in JP-A-2007-92086 can be exemplified.
本発明において、環状ポリスルフィドの配合量は、ジエン系ゴム１００重量部に対し、１〜１０重量部、好ましくは１．５〜８重量部にするとよい。環状ポリスルフィドの配合量が１重量部未満であると、ドライグリップ性能を高いレベルで長く持続する効果及び耐ブローアウト性を向上する効果が得られない。また粘着性付与樹脂を配合したゴム組成物の耐摩耗性低下を十分に抑制することができない。なお環状ポリスルフィドの配合量が１０重量部を超えると走行初期のグリップ性能が低下する。 In the present invention, the amount of the cyclic polysulfide is 1 to 10 parts by weight, preferably 1.5 to 8 parts by weight, based on 100 parts by weight of the diene rubber. When the blending amount of the cyclic polysulfide is less than 1 part by weight, the effect of maintaining the dry grip performance for a long time at a high level and the effect of improving the blowout resistance cannot be obtained. Moreover, the abrasion resistance fall of the rubber composition which mix | blended tackifying resin cannot fully be suppressed. If the amount of the cyclic polysulfide exceeds 10 parts by weight, the grip performance at the initial stage of travel is lowered.
本発明のタイヤトレッド用ゴム組成物において、上記式（Ｉ）の環状ポリスルフィドは加硫剤として作用する。加硫剤は、環状ポリスルフィド及び他の加硫剤を共に使用する。他の加硫剤は、硫黄である。硫黄の配合量は、ジエン系ゴム１００重量部に対し、０．１〜５重量部、好ましくは０．５〜４重量部にするとよい。硫黄に対する環状ポリスルフィドの重量比（環状ポリスルフィド／硫黄）は３／１〜１０／１、より好ましくは３／１〜４／１にする。（環状ポリスルフィド／硫黄）の重量比が３／１より小さいとドライグリップ性能を高いレベルで長く持続する効果及び耐ブローアウト性を向上する効果が得られず、耐摩耗性も低下する。また、この重量比が１０／１より大きいと走行初期のグリップ性能が低下する。 In the rubber composition for a tire tread of the present invention, the cyclic polysulfide of the above formula (I) acts as a vulcanizing agent. Vulcanizing agent, use both cyclic polysulfide and other vulcanizing agents. Other vulcanizing agent is sulfur. The amount of sulfur is 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the diene rubber . The weight ratio of the cyclic polysulfide for sulfur (cyclic polysulfide / sulfur) is 3/1 to 10/1, more preferably 3/1 to 4/1. When the weight ratio of (cyclic polysulfide / sulfur) is smaller than 3/1, the effect of maintaining the dry grip performance at a high level for a long time and the effect of improving the blowout resistance cannot be obtained, and the wear resistance is also lowered. On the other hand, if the weight ratio is larger than 10/1, the grip performance at the initial stage of travel is lowered.
タイヤトレッド用ゴム組成物は、カーボンブラックを配合することによりゴム剛性を大きくすると共に発熱性を高くしドライグリップ性能を高くする。カーボンブラックとしては、窒素吸着比表面積（Ｎ2ＳＡ）が２２０〜３５０ｍ2／ｇ、より好ましくは２２０〜３２０ｍ2／ｇのものを使用する。カーボンブラックの窒素吸着比表面積が２２０ｍ2／ｇ未満の場合には、ドライグリップ性能が十分に得られない。また、ゴム組成物のゴム強度が不足し、耐摩耗性が悪化する。窒素吸着比表面積が３５０ｍ2／ｇを超えると走行開始直後のドライグリップ性能が低下すると共に、耐熱ダレ性及び耐ブローアウト性が悪化する。また、ゴム粘度が高くなることにより加工性が悪化し製造上好ましくない。カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ）は、ＪＩＳ Ｋ６２１７−２に準拠して求めるものとする。 The tire tread rubber composition increases the rigidity of the rubber and increases the heat generation property and the dry grip performance by adding carbon black. Carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 220 to 350 m 2 / g, more preferably 220 to 320 m 2 / g is used. When the nitrogen adsorption specific surface area of carbon black is less than 220 m 2 / g, the dry grip performance cannot be sufficiently obtained. Moreover, the rubber strength of the rubber composition is insufficient, and the wear resistance is deteriorated. When the nitrogen adsorption specific surface area exceeds 350 m 2 / g, the dry grip performance immediately after the start of running deteriorates, and the heat sag resistance and blowout resistance deteriorate. Moreover, processability deteriorates due to the increased rubber viscosity, which is not preferable in production. The nitrogen adsorption specific surface area (N 2 SA) of carbon black is determined according to JIS K6217-2.
カーボンブラックの配合量は、ジエン系ゴム１００重量部に対し、１００〜１５０重量部、より好ましくは１００〜１３０重量部にする。カーボンブラック配合量が１００重量部未満であるとゴム剛性及びドライグリップ性能が不足する。また、カーボンブラック配合量が１５０重量部を超えると、発熱によるゴムの剛性低下が起きやすくなり、ドライグリップ性能の持続性が低くなる。 The amount of carbon black, relative to diene rubber 100 parts by weight, 100-150 parts by weight, more preferably you in 100-130 parts by weight. If the carbon black content is less than 100 parts by weight, the rubber rigidity and dry grip performance are insufficient. On the other hand, when the blending amount of carbon black exceeds 150 parts by weight, the rigidity of the rubber is easily lowered due to heat generation, and the durability of the dry grip performance is lowered.
本発明のタイヤトレッド用ゴム組成物には、カーボンブラック以外の無機充填剤を配合してもよい。無機充填剤としては、例えば、シリカ、クレー、炭酸カルシウム、水酸化アルミニウム、マイカ、タルク等を例示することができる。また、ゴム組成物には、加硫促進剤、老化防止剤、可塑剤、カップリング剤などのゴム組成物に一般的に使用される各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練してゴム組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。本発明のゴム組成物は、公知のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用して、上記各成分を混合することによって製造することができる。 You may mix | blend inorganic fillers other than carbon black with the rubber composition for tire treads of this invention. Examples of the inorganic filler include silica, clay, calcium carbonate, aluminum hydroxide, mica, talc and the like. The rubber composition can contain various additives generally used in rubber compositions such as a vulcanization accelerator, an anti-aging agent, a plasticizer, and a coupling agent. The rubber composition can be kneaded by a conventional method and used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used. The rubber composition of the present invention can be produced by mixing each of the above components using a known rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
本発明のタイヤトレッド用ゴム組成物は、競技用タイヤや一般用の高性能タイヤのトレッド部に使用するのが好適である。このタイヤトレッド用ゴム組成物を使用してトレッド部を構成した空気入りタイヤは、耐摩耗性を維持しながら走行初期からのドライグリップ性能が優れると共に、優れたドライグリップ性能の高い持続性を可能にすると共に、耐ブローアウト性を向上することができる。 The rubber composition for a tire tread of the present invention is preferably used for a tread portion of a racing tire or a general-purpose high-performance tire. Pneumatic tires that use this tire tread rubber composition to form the tread part have excellent dry grip performance from the beginning of running while maintaining wear resistance, and high durability with excellent dry grip performance. In addition, the blowout resistance can be improved.
以下に、実施例を挙げて本発明を説明するが、これにより本発明の範囲が制限を受けるものではない。 Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited thereby.
表１，２に示す配合からなる１５種類のゴム組成物（実施例１〜３、比較例１〜１２）を、それぞれ硫黄、加硫促進剤及び環状ポリスルフィドを除く配合成分を秤量し、１６Ｌのバンバリーミキサーで１０分間混練し、温度１６０℃でマスターバッチを放出し室温冷却した。このマスターバッチを１６Ｌのバンバリーミキサーで、硫黄、加硫促進剤及び環状ポリスルフィドを加え混合し、タイヤトレッド用ゴム組成物を調製した。得られた１５種類のゴム組成物を使用してトレッド部を構成したタイヤサイズ１９５／５５Ｒ１５の空気入りタイヤを製作した。 15 types of rubber compositions (Examples 1 to 3 and Comparative Examples 1 to 12 ) having the formulations shown in Tables 1 and 2 were weighed for the components except for sulfur, vulcanization accelerator, and cyclic polysulfide, respectively. The mixture was kneaded with a Banbury mixer for 10 minutes, and the master batch was discharged at a temperature of 160 ° C. and cooled at room temperature. This master batch was mixed with a 16 L Banbury mixer by adding sulfur, a vulcanization accelerator, and a cyclic polysulfide to prepare a rubber composition for a tire tread. A pneumatic tire having a tire size of 195 / 55R15 having a tread portion was manufactured using the 15 types of rubber compositions obtained.
得られた空気入りタイヤを、それぞれサイズ１５×６Ｊのリムに組み、空気圧１５０ｋＰａとし、２０００ｃｃの国産車両に装着し、テストドライバーがドライ条件のサーキットコース（１周２ｋｍ）を連続周回したときの周回毎のラップタイムを計測し、下記の方法により走行初期のドライグリップ性能及びドライグリップ性能の持続性及び耐ブローアウト性を評価した。また、下記の方法により耐摩耗性を評価した。 The resulting pneumatic tires are assembled on rims of size 15x6J, mounted on a 2000cc domestic vehicle with a pneumatic pressure of 150kPa, and the lap when the test driver circulates continuously on a dry circuit course (1km 2km) Each lap time was measured, and the dry grip performance at the beginning of running, the durability of the dry grip performance and the blowout resistance were evaluated by the following methods. Moreover, abrasion resistance was evaluated by the following method.
走行初期のドライグリップ性能
ドライ条件のサーキットコースを連続走行したときの計測３ラップ目での周回タイムを計測した。得られた結果は、３ラップ目の周回タイムの逆数を算出し、比較例１の空気入りタイヤを１００とする指数として、表１，２の「初期グリップ性能」の欄に示した。この指数が大きいほど走行初期からのドライグリップ性能が優れることを意味する。
Dry grip performance at the beginning of running Measurement when running continuously on a circuit course in dry conditions The lap time at the third lap was measured. The obtained results are shown in the column of “Initial grip performance” in Tables 1 and 2 by calculating the reciprocal of the lap time of the third lap and using the pneumatic tire of Comparative Example 1 as an index of 100. The larger the index, the better the dry grip performance from the beginning of running.
ドライグリップ性能の持続性
ドライ条件のサーキットコースを連続走行したときの計測１５ラップ目での周回タイムを計測した。得られた結果は、１５ラップ目の周回タイムの逆数を算出し、比較例１の空気入りタイヤを１００とする指数として、表１，２の「グリップ持続性能」の欄に示した。この指数が大きいほどドライグリップ性能を持続する性能が優れることを意味する。
Persistence of dry grip performance Measurement when running continuously on a circuit course in dry conditions The lap time at the 15th lap was measured. The obtained results are shown in the column of “Grip Sustainability” in Tables 1 and 2 by calculating the reciprocal of the lap time of the 15th lap and taking the pneumatic tire of Comparative Example 1 as 100. The larger the index, the better the performance of maintaining the dry grip performance.
耐ブローアウト性
ドライ条件のサーキットコースを連続走行したときのタイヤのブローアウトを目視で判断し、ブローアウトが発生するまでの周回数を求めた。得られた結果は、比較例１の空気入りタイヤの周回数を１００とする指数として、表１，２の「耐ブローアウト性」の欄に示した。この指数が大きいほど耐ブローアウト性能が優れることを意味する。
Blow-out resistance The tire blow-out was judged visually when continuously running on a circuit course under dry conditions, and the number of laps until blow-out occurred was determined. The obtained results are shown in the “Blowout resistance” column of Tables 1 and 2 as an index with the number of laps of the pneumatic tire of Comparative Example 1 as 100. A larger index means better blowout resistance.
耐摩耗性
ドライ条件のサーキットコースを計測２０ラップの連続走行した後、空気入りタイヤのトレッド部における陸部の高さを測定した。得られた結果は、比較例１の空気入りタイヤを１００とする指数として、表１，２の「耐摩耗性」の欄に示した。この指数が大きいほど耐摩耗性が優れることを意味する。
Abrasion resistance After measuring 20 laps continuously on a circuit course under dry conditions, the height of the land portion in the tread portion of the pneumatic tire was measured. The obtained results are shown in the “Abrasion resistance” column of Tables 1 and 2 as an index with the pneumatic tire of Comparative Example 1 as 100. Higher index means better wear resistance.
なお、表１，２において使用した原材料の種類を下記に示す。
ＳＢＲ：乳化重合スチレンブタジエンゴム、ガラス転移温度−２０℃（日本ゼオン社製ＮＩＰＯＬ ９５２９、ゴム１００重量部に対しアロマオイル５０重量部添加の油展品）
カーボンブラック１：新日化カーボン社製ニテロン４１５ＵＤ、窒素吸着比表面積（Ｎ２ＳＡ）２２０ｍ２／ｇ
カーボンブラック２：東海カーボン社製シースト９Ｍ、窒素吸着比表面積（Ｎ２ＳＡ）１４０ｍ２／ｇ
粘着性付与樹脂１：テルペンフェノール樹脂、軟化点１６０℃、ヤスハラケミカル社製ＹＳポリスターＴ１６０
粘着性付与樹脂２：芳香族変性テルペン樹脂、軟化点８５℃、ヤスハラケミカル社製ＹＳレジンＴＯ８５
アロマオイル：昭和シェル石油社製デゾレックス３号
酸化亜鉛：東邦亜鉛社製銀嶺Ｒ
ステアリン酸：日油社製ビーズステアリン酸ＹＲ
老化防止剤：フレキシス社製ＦＬＥＣＴＯＬ ＴＭＱ
加硫促進剤：大内新興化学工業社製ノクセラーＴＯＴ−Ｎ
硫黄：鶴見化学工業社製金華印油入微粉硫黄
環状ポリスルフィド：式（Ｉ）において、Ｒ＝（ＣＨ２）２Ｏ（ＣＨ２）２、Ｘ（平均）＝４、ｎ＝２〜３の環状ポリスルフィド、１，２−ジクロロエタン１．９８ｇ（０．０２ｍｏｌ）と３０％多硫化ソーダ（Ｎａ２Ｓ４）水溶液１１９７ｇ（２ｍｏｌ）をトルエン（５００ｇ）に加えた後、更にテトラブチルアンモニウムブロマイド０．６４ｇ（０．１ｍｏｌ）を入れ、５０℃で２時間反応させた。続いて反応温度を９０℃に上げ、ジクロロエチルホルマール３１１ｇ（１．８ｍｏｌ）をトルエン３００ｇに溶かした溶液を１時間かけて滴下し、更に５時間反応させた。反応後、有機層を分離し、減圧下９０℃で濃縮して、上述した還状ポリスルフィドを４０５ｇ得た（収率９６．９％）。
The types of raw materials used in Tables 1 and 2 are shown below.
SBR: Emulsion-polymerized styrene butadiene rubber, glass transition temperature -20 ° C (NIPOL 9529 manufactured by Nippon Zeon Co., Ltd., an oil exhibition with 50 parts by weight of aroma oil added to 100 parts by weight of rubber)
Carbon black 1: Niteron 415UD made by Nisshin Carbon Co., Nitrogen adsorption specific surface area (N 2 SA) 220 m 2 / g
Carbon black 2: Toast carbon company's seast 9M, nitrogen adsorption specific surface area (N 2 SA) 140 m 2 / g
Tackifying resin 1: terpene phenol resin, softening point 160 ° C, YS Polystar T160 manufactured by Yasuhara Chemical Co., Ltd.
Tackifying resin 2: Aromatic modified terpene resin, softening point 85 ° C., YS resin TO85 manufactured by Yasuhara Chemical Co., Ltd.
Aroma oil: Desolex No. 3 zinc oxide manufactured by Showa Shell Sekiyu KK: Ginbae R manufactured by Toho Zinc Co., Ltd.
Stearic acid: NOF Beads Stearic Acid YR
Anti-aging agent: FLECTOL TMQ manufactured by Flexis
Vulcanization accelerator: NOCELLER TOT-N manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Fine powder sulfur cyclic polysulfide containing Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd .: In formula (I), R = (CH 2 ) 2 O (CH 2 ) 2 , X (average) = 4, n = 2 to 3 cyclic polysulfide 1,2-dichloroethane 1.98 g (0.02 mol) and 30% sodium polysulfide (Na 2 S 4 ) aqueous solution 1197 g (2 mol) were added to toluene (500 g), and then tetrabutylammonium bromide 0.64 g ( 0.1 mol) was added and reacted at 50 ° C. for 2 hours. Subsequently, the reaction temperature was raised to 90 ° C., and a solution prepared by dissolving 311 g (1.8 mol) of dichloroethyl formal in 300 g of toluene was dropped over 1 hour, and the reaction was further continued for 5 hours. After the reaction, the organic layer was separated and concentrated at 90 ° C. under reduced pressure to obtain 405 g of the above-mentioned returned polysulfide (yield 96.9%).
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| WO2013132631A1 (en) * | 2012-03-08 | 2013-09-12 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP5998310B1 (en) | 2014-11-27 | 2016-09-28 | 株式会社ブリヂストン | Rubber composition, method for producing the same, and tire |
| JP6724377B2 (en) * | 2016-01-19 | 2020-07-15 | 横浜ゴム株式会社 | Pneumatic tire |
| JP7294393B1 (en) * | 2021-12-07 | 2023-06-20 | 横浜ゴム株式会社 | Rubber composition for tire |
| CN114232041B (en) * | 2022-01-17 | 2023-11-21 | 中国计量大学 | High-depth-diameter-ratio blind hole copper filling electroplating solution and preparation method thereof |
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| JP3996777B2 (en) * | 2002-01-22 | 2007-10-24 | 住友ゴム工業株式会社 | Tread rubber for tires |
| JP4290725B2 (en) * | 2003-10-14 | 2009-07-08 | 横浜ゴム株式会社 | Rubber composition for tire tread containing cyclic polysulfide as vulcanizing agent and pneumatic tire using the same |
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